Plasticized elastomer compositions



Patented Mar. 8, 1949 PLASTICIZED ELASTOMER COMPOSITIONS Philip F. Tryon, Terre Haute, Ind., asslgnor to Commercial Solvents Corporation, Terre Haute, Ind., a corporation of Maryland No Drawing. Application March 16, 1945, Serial No. 583,170

8 Claims. (Cl. 260-4304) This invention relates to plasticized elastomer compositions and more particularly to such compositions in which so-called synthetic rubbers are plasticized or softened with softening agents of the class of (acyloxymethyl) oxazolines represented by the formula given below:

wherein R may be an alkyl or phenyl radical, R," is a member selected from the group consisting of methyl, ethyl and alkanecarbonyloxymethyl radicals, and R is an alkanecarbonyloxymethyl radical.

In the manufacture and compounding of rubber and synthetic rubber, it is necessary to bring the compound into a plastic state so that pigment, fillers, and the like can be incorporated therein and so that the product can be molded into the desired shape before vulcanizing such as by extrusion and the like. In the case of natural rubber, simple heating by friction milling on a roller mill is usually suflicient to induce the necessary degree of plasticity for these purposes.

The so-called synthetic rubbers or synthetic elastomers, on the other hand, do not respond easily to milling treatment and often becomes hard and brittle or crumble when subjected to such milling. Furthermore, many addition agents which serve to soften the compound and permit it to extrude readily are of such character that the extruded material fails, to remain in the extruded shape and instead tends to return to its original shape after extrusion.

It is, therefore, an object of my invention to provide a class of compounds which not only soften and plasticize synthetic rubbers of the type described hereinafter but which cause a retention of the extruded shape without substantial loss to tensile and elongation characteristics.

These objects are accomplished by my invention in which (acyloxymethyl)oxazolines of the class described are utilized as plasticizers for synthetic elastomers and impart their beneficial softening properties without damage to the tensile strength and elongation characteristics of the resulting composition.

The softening agents of my invention may be employed in conjunction with any of the synthetic rubbers prepared by polymerization of 1,3- butadiene alone or 1,3-butadiene copolymerized with other polymerizable monomers which contain the polymeric structure,

among which may be mentioned the aryl oleflnes such as styrene and vinyl naphthalene, the alpha methylene carboxylic acids and their esters, nitriles, and amides, such as acrylic acid, methyl methacrylate, acrylonitrile, methacrylonitrile, methacrylamide, and isobutylene, methyl vinyl ether, etc. My softening agents are especially effective when utilized to plasticize butadieneacrylonitrile type copolymers which are usually recognized as among the most diflicult of the elastomers to plasticize satisfactorily.

As illustrative of compounds coming within the above formula, may be mentioned 2-pentyl-' 4,4l-bis (caprooxmnethyl) -2'-oxazoline; 2-heptyl- 4-methyl-4capry1oxymethyl 2 oxazoline; 2- heptyl-4-ethyl-4-capryloxymethyl-2 oxazoline; 2-heptyl-4,4-bis(capryloxymethyl) 2-oxazoline; 2-nonyl-4-methyl-4-caproxymethyl 2 oxazoline; 2-nonyl-4-ethyl-4-caproxymethyl-2-oxazoline; 2,4diethyl-4-propionoxymethyl-2 oxazoline; 2-phenyl-4-lauroxymethyl-4 methyl 2- oxazoline; 2-undecyl-4 propionoxymethyl 4- methyl-2-oxazoline; and the like.

The (acyloxymethyl)oxazolines may be prepared by any desired procedure, for example, by the method described in my copending application Serial No. 553,671, filed September 11, 1944, in which a dior poly-hydroxy primary amine, and monocarboxylic acid are reacted according to a scheme in which all the steps of the reaction take place in a single operation. Or the compounds of my invention may be prepared as described in copending application Serial No. 482.758, filed April 12, 1943, now U. S. Patent No. 2,372,409, in which the preperation of (acyloxymethyDoxazolines from esters of nitrohydroxy compounds is described.

The amount of (acyloxymethyl) oxazoline to be used as plasticizer will vary with the relative difliculty of plasticization and the particular elastomer involved and with the degree of softness or plasticity desired. In general my softeners can be employed in a wide range of pro-' portions and preferably within the range of concentrations varying from about 10 to 45 parts by weight of plasticizer for each parts by weight of elastomer.

The plasticizers of my invention impart in general a high degree of plasticity to elastomer conipositions, without appreciably reducing the tensile plasticizers of the type herein described all result in extruded or molded compositions which retain their molded shape satisfactorily.

scribed above the "nerve of the stock was great- 1y reduced, that is, the tendency to return to its undistorted state was reduced to such an extent that stocks so treated were of such character as A convenient method for evaluating the eflecs to be readily adapted for use in commercial extrutiveness of plasticizing compositions comprises sion processes. milling the composition in a standard rubber for- While the above describes the preferred embodimula on a conventional rubber mill and then ments of my invention, it is to be understood that measuring the ease of extrusion as indicated by departures may be made therefrom within the the extrusion time at various pressures in an '10 scope of the specification and claims. extrusion plastometer, for example, in an instru- What is claimed is: ment and according to a method similar to that 1. A plasticized elastomer composition comdescribed by J. H. Dillon in RubberChemistry prising a rubber-like synthetic elastomer selected and Technology, vol. 9, pages 496-501, July, 1936. from the group consisting of 1,3-butadiene poly- In order to evaluate the efiect of plasticizer on 15 mers and copolymers of 1,3-butadiene with the tensile and elongation properties of the elasanother monomer having the following structomer, samples of the milled sheet are tested for ture: these factors in the standard Scott tensile tester. H,c=o

As illustrative of my invention, tensile, elonga- 2o tion and extrusion values as measured bythe inand a plastieizer having the following st u t al strument above referred to were run on a number formula! of representative esters of hydroxymethyl oxazo- R lines of the class described. a

The plasticizer was added in each case in the 26 indicated amount in the standard formula given o below and milled into the stock in the conven- H gh- 6 tional manner. i

Test composition 30 wherein R represents a member selected from Parts by weight the group consisting of alkyl and phenyl radicals, Butadiene acrylomtrue copolymer 100 R is a member selected from the group consist- Zmc oxide ing of methyl, ethyl and alkanecarbonyloxystearic Acid 1 methyl radicals, and R is an alkanecarbonyl- Benzothiazyldisulfide 1.5 35 oxymethyl radlca'l' Sulfur L5 2. A plasticized elastomer composition com- Carbon 5o prising a rubber-like synthetic elastomer selected plasticizer 30 from the group consisting of 1,3-butadiene polymers and copolymers of 1,3-butadiene with Total w another monomer having the following structure: After milling, part of each sample was subject- H,c- -g ed to tensile and elongation tests, part was tested g in the extrusion plastometer with the results given and a plasticizer comprising 2-pentyl-4,4-bisbelow: (caprooxymethyl) -2-oxa zoline.

Table Extrusion Piasticizer Elastomer Tensile Elong. Time at None Hycar QR" 2,280 247 866M360 D0 Perbnnam l, 550 215 1, 650 2-Pentyl-4,4-bis-(caprooxymethyl)-2-oxazoline Hycar O 2,300 417 Do Pei-bunch. 2, 090 305 4 2-Heoty1 4 methyl 4 capryloxymethyl 2 oxazolin Hycar OR 1,400 207 28 o Perbunan. 1,840 440 9 2-Heptyl-4,4-bis-(capryloxymethyD-2-oxazoline do 2,120 465 6 2-NonyI-4-methyl-4-cnproxymethyl-2-oxazoline do l, 430 405 5 Z-Nonyl-4-ethyI-4-caproxymcthyl-2-oxazoline- .-.do l, 500 410 3 2,4-T iethyli-propionoxymethyl-2-oxazoline Hycar 0R 3,100 550 4 2-Pheny1-4-lauroxymethyl-4-methyl-2-oxazoline. -do.- 2,800 390 2-Undccyl-4-nmpionoxymethyl-4-methyl-2-oxazoline .do..... 2.470 476 14 Dibutyl phthnlate do 2,980 480 19 Tricresyl phosphate .do. 2, 545 395 more plastic the composition, the more rapidly will it extrude at a given pressure. It will be observed that in the table above the plasticizing efiects are high and in most cases are superior to the controls, dibutyl phthalate and tricresyl phosphate, which are usually run in conjunction with such tests for comparison. It will also be observed that in most cases the composition shows little or no loss in tensile and elongation over the original unplasticized batch.

3. A plasticized elastomer composition comprising a. rubber-like synthetic elastomer selected from the group consisting'of 1,3-butadiene polymers and copolymers of I 1,3-butadiene with another monomer having the following structure:

and a plasticizer comprising 2-nonyl-4-ethyl-4- caproxymethyl-2-oxazoline.

4. A plasticized elastomer composition comprising a rubber-like synthetic elastomer selected In all of the uncured plasticized stocks defrom the group consisting of 1,3-butadiene poly:

' methyl.

mersand copolyj'mersof 1,3-butadiene with another monomer having the following structure:

and a plasticizer comprising 2,4-diethyl-4-propionoxymethyl-2-dxazo1ine.

5. A plasticized, elastomer composition comprising a rubber-like butadiene-acrylonitrile copolymer, and a. plesticizer having the following structural formula:

wherein R is a member selected from the group consisting of alkyl and phenyl radicals, R is a member selected from the group consisting of ethyl and alkanecarbonyloxymethyl ms and R is an alkanecarbonyloxymethyl PHILIP F. TRYON.

REFERENCES CITED The following references are of record in the file of this patent:

Karrer, Organic Chemistry. page 67, published 1938, Elsvier New York. Nordeman Publishing Company Inc., New York. N. Y. 

